Pesticidal phenylhydrazinephosphates

ABSTRACT

Compounds having the formula: ##STR1## wherein R is C 1  -C 4  alkoxy, C 1  -C 4  alkyl, hydrogen, halogen, or C 1  -C 4  alkylthio; R 1  is phenyl, phenoxy, or benzyl, the phenyl ring of each substituent being optionally substituted with one or more of halogen, nitro, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkyl or di(C 1  -C 4  alkyl)amino; and R 2  is branched or straight-chained, C 1  -C 6  alkyl, C 1  -C 6  alkoxy, C 3  -C 6  cycloalkoxy, C 1  -C 6  haloalkyl, alkoxyalkyl, C 1  -C 6  alkenyl, C 1  -C 6  alkylthio, (C 1  -C 6  alkoxy)carbonyl, C 1  -C 6  alkylamino, C 1  -C 6  haloalkoxy, or C 3  -C 6  cycloalkyl. These compounds are effective for controlling mites.

FIELD OF THE INVENTION

This invention is directed to novel phenylhydrazinephosphate derivativeswhich exhibit activity as miticides.

BACKGROUND OF THE INVENTION

Destruction of crops by mites presents a serious problem to agriculture.A wide variety of field crops are in need of protection from mitesincluding such valuable crops as corn and cotton. In addition, fruits,nuts, ornamentals and seed bed crops such as almonds, apples, pears,citrus fruit and grapes may also require protection from the ravages ofsuch mites. More particularly, the development of pesticides which areeffective as both ovicides, larvicides and adulticides are of interest.

Chemical Abstracts 108(19):163280d describes certain alkylphenylhydrazinecarboxylates and the preparation and acaricidal usethereof. U.S. Pat. No. 4,725,302 describes certain substitutedphenylhydrazines and phenyloxadiazolinones and pesticidal uses thereof.European Patent 067 471 describes certain 7-substituted2,3-dihydrobenzofurans, their preparation, and their use as pesticidesor chemical intermediates. DerWent Abstract 88-312695/44 describescertain arylhydrazides of trifluoroacetic acid that have fungicidal,bacteriocidal, acaricidal, and antiseptic activity. U.S. Pat. No.5,367,093 describes certain insecticidal phenylhydrazine derivatives.

It is the purpose of this to provide novel hydrazine derivatives usefulas miticides and nemotacides.

SUMMARY OF THE INVENTION

The present invention relates to a compound having the formula: ##STR2##wherein R is C₁ -C₄ alkoxy, C₁ -C₄ alkyl, hydrogen, halogen, or C₁ -C₄alkylthio; R¹ is phenyl, phenoxy, or benzyl, the phenyl ring of eachsubstituent being optionally substituted with one or more of halogen,nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkyl or di(C₁ -C₄alkyl)amino; and R² is branched or straight-chained, C₁ -C₆ alkyl, C₁-C₆ alkoxy, C₃ -C₆ cycloalkoxy, C₁ -C₆ haloalkyl, alkoxyalkyl, C₁ -C₆alkenyl, C₁ -C₆ alkylthio, (C₁ -C₆ alkoxy) carbonyl, C₁ -C₆ alkylamino,C₁ -C₆ haloalkoxy, or C₃ -C₆ cycloalkyl. The compounds of formula (I)and (II), and compositions comprising them, have been found to be plantprotecting agents for the control of mites.

DETAILED DESCRIPTION OF THE INVENTION

Preferred are those compounds of formula (I) and (II) wherein R is C₁-C₄ alkoxy or C₁ -C₄ alkyl, R¹ is phenyl, and R² is, branched orstraight-chained, C₁ -C₄ alkyl or C₁ -C₄ alkoxy. More preferred is thecompound of formula (I) wherein R is C₁ -C₄ alkoxy, R¹ is phenyl, and R²is branched or straight-chained C₁ -C₄ alkyl. Particularly preferred isthe compound of formula (I) wherein R is methoxy, R¹ is phenyl, and R²is ethyl or propyl.

The compounds of structure (I) of the instant invention may be preparedby reacting a hydrazine derivative of the formula ##STR3## wherein R andR¹ are as described above, and a halophosphate of the formula ##STR4##wherein R² is as described above.

The miticidal compositions of this invention comprise (a) a compoundhaving a structure within that of formula (I) or (II) above and (b) asuitable carrier. Such suitable carriers may be solid or liquid innature.

Suitable liquid carriers may be comprised of water, alcohols, ketones,phenols, toluene and xylenes. In such formulations, additivesconventionally employed in the art may be utilized such as, for example,one or more surface active agents and/or inert diluents, to facilitatehandling an application of the resulting miticide composition.

The miticidal compositions may alternatively comprise solid carrierstaking the form of dusts, granules, wettable powders, pastes, aerosols,emulsions, emulsifiable concentrates, and water-soluble solids.

For example, the miticidal compounds of this invention may be applied asdusts when admixed with or absorbed onto powdered solid carriers, suchas mineral silicates, e.g., mica, talc, pyrophyllite and clays, togetherwith a surface-active dispersing agent so that a wettable powder isobtained which then is applicable directly to the loci to be treated.Alternatively, the powdered solid carrier containing the compoundadmixed therewith may be dispersed in water to form a suspension forapplication in such form.

Granular formulations of the compounds, suitable for application bybroadcasting, side dressing, soil incorporation or seed treatment, aresuitably prepared using a granular or pellitized form of carrier such asgranular clays, vermiculite, charcoal or corn cobs.

Alternatively, the miticidal compounds may be applied in liquids orsprays when utilized in a liquid carrier, such as in a solutioncomprising a compatible solvent such as acetone, benzene, toluene orkerosene, or as dispersed in a suitable non-solvent medium, for example,water. Another method of application to loci to be treated is aerosoltreatment, for which the compound may be dissolved in an aerosol carrierwhich is a liquid under pressure but which is a gas at ordinarytemperature (e.g., 20° C.) and atmospheric pressure. Aerosolformulations may also be prepared by first dissolving the compound in aless volatile solvent and then admixing the resulting solution with ahighly volatile liquid aerosol carrier.

For pesticidal treatment of plants (such term including plant parts),the compounds of the invention preferably are applied in aqueousemulsions containing a surface-active dispersing agent which may benon-ionic, cationic or anionic. Suitable surface-active agents includethose known in the art, such as those disclosed in U.S. Pat. No.2,547,724 (columns 3 and 4). The compounds of the invention may be mixedwith such surface-active dispersing agents, with or without an organicsolvent, as concentrates for the subsequent addition of water to yieldaqueous suspensions of the compounds at desired concentration levels.

In addition, the compounds may be employed with carriers whichthemselves are pesticidally active, such as insecticides, acaricides,fungicides or bactericides.

It will be understood that the amount of the pesticidally activecompound in a given formulation will depend upon the specific pest to becombatted, as well as upon the specific chemical composition andformulation of the compound being employed, the method of applying thecompound/formulation and the locus of treatment so that the pesticidallyeffective amount of the compound may vary widely. Generally, however,concentrations of the compound as the active ingredient in pesticidallyeffective formulations may range from about 0.1 to about 95 percent byweight. Spray dilutions may be as low as a few parts per million, whileat the opposite extreme, full strength concentrates of the compound maybe usefully applied by ultra low volume techniques. Concentration perunit area, where plants constitute the loci of treatment, may rangebetween about 0.01 and about 50 pounds per acre, with concentrations ofbetween about 0.1 and about 10 pounds per acre preferably being employedfor crops such as corn, and the like.

To combat mites, sprays of the compounds may be applied to the mitesdirectly and/or to plants upon which they feed or nest.

Harmful mites attack a wide variety of plants, including both ornamentaland agricultural plants and inflict damage by consuming roots and/orfoliage, withdrawing vital juices from the plants, secreting toxins andoften by transmitting diseases. The compounds of the present inventionmay be advantageously utilized to minimize or prevent such damage. Thespecific methods of application, as well as the selection andconcentration of these compounds will, of course, vary depending uponsuch circumstances as geographic area, climate, topography, planttolerance, etc. For specific circumstances, one skilled in the art mayreadily determine the proper compound, concentration and method ofapplication by routine experimentation.

The compounds of the invention are particularly useful as miticides, forfoliar application.

The following examples are presented to further illustrate the presentinvention.

EXAMPLES Example 1 Preparation of dipropyl2-(4-methoxy-[1,1'-biphenyl]-3-yl)-hydrazinephosphate (Compound 1)

To 2.5 g of 4-methoxy-[1,1'-biphenyl]-3-amine were added 100 mL of waterand 50 mL of concentrated HCL and the stirred mixture was cooled to -5°C. A solution of 1 g of sodium nitrite in 10 mL of water was then addeddropwise, maintaining a temperature of -5° C. After this addition, themixture was stirred at -5° C. for 1 hour. A solution of 10 g of stannouschloride in 20 mL of concentrated HCL was added quickly to the reactionmixture which was then stirred for 1 hour, then neutralized with sodiumhydroxide and extracted with dichloromethane. Evaporation of thedichloromethane gave 1.5 g of an oil which was then dissolved in 100 mLof toluene. To this solution was added 2 g of dipropyl chlorophosphateand the resulting mixture was refluxed for 2 hours. Upon evaporation ofthe toluene, 3 g of a waxy solid remained.

Compound 2 shown in Table 1 below was prepared using an analogousprocedure. Compounds 1 and 2 are characterized by their proton NMRcharacteristics.

                  TABLE I                                                         ______________________________________                                         ##STR5##                      (I)                                            Compound                       NMR Data                                       No.     R        R.sup.1                                                                              R.sup.2                                                                              (CDCL.sub.3 PPM)                               ______________________________________                                        1       OCH.sub.3                                                                              C.sub.6 H.sub.5                                                                      C.sub.3 H.sub.7                                                                      t(6)1.0; m(4)1.9; s(3)3.9;                                                    m(4)4.1; m(8)7.0-7.6                           2       OCH.sub.3                                                                              C.sub.6 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      t(6)1.0; s(3)3.9; q(6)4.1;                                                    m(8)7.0-7.6                                    ______________________________________                                    

Example 2 Preparation of Formulations

The remaining examples relate to the pesticidal use of the compounds ofthis invention. In all these examples a stock solution for each of thecompounds was prepared at 3000 ppm by dissolving 0.3 gram of eachcompound to be tested in 10 ml of acetone and adding 90 ml of distilledwater plus four drops of ethoxylated sorbitan monolaurate, or a simliarsuitable wetting agent, to provide a stock solution for each testedcompound. For each example that follows, this stock solution was usedand the specificied dilutions made. All the tests discussed below, whichinvolved treatment with compounds of this invention at concentrations of500 and 40 ppm, were always repeated with controls, in which the activecompound was not provided, to permit a comparison upon which the percentcontrol was calculated.

Example 3 Mite Adulticide and Mite Ovicide/Larvicide Tests

One day before treatment, a "FIG. 8" configuartion of tree tanglefootwas applied to each of two cowpea primary leaves, one from each of twoplants in a pot. In each figure, the circle nearer the stem wasdesignated for the mite ovicide/larvicide test and the circle furtherfrom the stem was designated for the mite adulticide test.

Groups of adult mites (Tetranychus urticae Koch) were transferred intoovicide circles one day before treatment and the females were allowed todeposit eggs until one hour before treatment when all mites wereremoved. Plants were sprayed to run off with a 1000 ppm solution dilutedfrom the 3000 ppm stock solution.

One day following treatment, groups of approximately 25 adult mites weretransferred into the adulticide rings. Five days later these rings wereexamined for live mites remaining on the leaves. The percent control wasestimated based on the number of mites surviving on the plants.

Nine days following treatment the ovicide/larvicide rings were examinedfor hatched eggs and living immature mites. The percent control wasestimated based on the number of eggs hatching and immature mitessurviving on the plants. When the treatment effect was to eggs, controlwas designated as ovicidal (O); when the treatment effect was toimmatures, control was designated as larvicidal (L).

Results of the mite adulticide (MI) and ovicide/larvicide (MIOLV) testsare presented in Table 2 below.

                  TABLE 2                                                         ______________________________________                                        Percent Control                                                               Compound No.     MI     MIOVL                                                 ______________________________________                                        1                100    100(O)                                                2                100     70(L)                                                ______________________________________                                    

What is claimed is:
 1. A compound of the formula: ##STR6## wherein R isC₁ -C₄ alkoxy, C₁ -C₄ alkyl, hydrogen, halogen, or C₁ -C₄ alkylthio; R¹is phenyl, phenoxy, or benzyl, the phenyl ring of each substituent beingoptionally substituted with one or more of halogen, nitro, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₁ -C₄ haloalkyl or di(C₁ -C₄ alkyl)amino; and R² isbranched or straight-chained, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₃ -C₆cycloalkoxy, C₁ -C₆ haloalkyl, alkoxyalkyl, C₁ -C₆ alkenyl, C₁ -C₆alkylthio, (C₁ -C₆ alkoxy) carbonyl, C₁ -C₆ alkylamino, C₁ -C₆haloalkoxy, or C₃ -C₆ cycloalkyl.
 2. A compound as recited in claim 1wherein R is C₁ -C₄ alkoxy or C₁ -C₄ alkyl.
 3. A compound as recited inclaim 2 wherein R is C₁ -C₄ alkoxy.
 4. A compound as recited in claim 3wherein R is methoxy.
 5. A compound as recited in claim 1 wherein R¹ isphenyl.
 6. A compound as recited in claim 1 wherein R² is, branched orstraight-chained, C₁ -C₄ alkyl or C₁ -C₄ alkoxy.
 7. A compound asrecited in claim 6 wherein R² is branched or straight-chained C₁ -C₄alkyl.
 8. A compound as recited in claim 7 wherein R² is ethyl orpropyl.
 9. A compound as recited in claim 1 of the formula ##STR7##wherein R, R¹ and R² are as defined in claim
 1. 10. A compound asrecited in claim 9 wherein R is C₁ -C₄ alkoxy or C₁ -C₄ alkyl, R¹ isphenyl, and R² is, branched or straight-chained, C₁ -C₄ alkyl or C₁ -C₄alkoxy.
 11. A compound as recited in claim 10 wherein R is C₁ -C₄alkoxy, R¹ is phenyl, and R² is branched or straight-chained C₁ -C₄alkyl.
 12. A compound as recited in claim 11 wherein R is methoxy, R¹ isphenyl, and R² is ethyl or propyl.
 13. A compound as recited in claim 1of the formula ##STR8## wherein R, R^(m) and R² are as defined inclaim
 1. 14. A miticidal composition comprising a miticidally effectiveamount of a compound as recited in claim 1 and an acceptable carrier.15. A miticidal composition comprising a miticidally effective amount ofa compound as recited in claim 9 and an acceptable carrier.
 16. Amiticidal composition comprising a miticidally effective amount of acompound as recited in claim 10 and an acceptable carrier.
 17. A methodfor controlling undesirable mites which comprises applying to a locus tobe protected a miticidally effective amount of a compound as recited inclaim
 13. 18. A method for controlling undesirable mites which comprisesapplying to a locus to be protected a miticidally effective amount of acompound as recited in claim
 1. 19. A method for controlling undesirablemites which comprises applying to a locus to be protected a miticidallyeffective amount of a compound as recited in claim
 9. 20. A method forcontrolling undesirable mites which comprises applying to a locus to beprotected a miticidally effective amount of a compound as recited inclaim 13.